CN105324407B - Active energy ray-curable composition - Google Patents

Abstract

The problem of the present invention be there is provided it is a kind of do not produce crack caused by cure shrinkage, hardness, marresistance, excellent impact resistance solidification compound.The present invention is a kind of active energy ray-curable composition, it is characterized in that, silane compound (II) represented containing make that following logical formula (I)s the represent, silane compound (I) with hydrolyzable silyl group and following logical formula (II)s, with hydrolyzable silyl group, by silane compound (II) relative to the mol ratio of silane compound (I) be set to less than 2.0 and be hydrolyzed in the basic conditions, be condensed obtained from weight average molecular weight 20, less than 000 condensation product (A) and photoacid generator (B), R¹‑(SiR² _a(OR³)_3-a)(I)R⁴‑Si(OR³)₃(II) OR for the silicon atom Direct Bonding, having with condensation product (A)³ORs of the molal quantity Y of base relative to the silicon atom Direct Bonding that the silane compound (I) and silane compound (II) with the raw material as condensation product (A) have³The ratio between the molal quantity X of base Y/X is less than 0.2.

Description

Active energy ray-curable composition

Technical field

The present invention relates to the manufacture method of a kind of active energy ray-curable composition, solidfied material, layered product and layered product.

Background technology

In recent years, in the field of hard conating, from the viewpoint of lightweight, low price, it is used as replacing for metal or glass In generation, widely carry out the research relevant with photocurable resin coating agent.Wherein, more report to have and produced using optical free radical Agent carries out the coating agent (patent document 1) of UV solidifications, but using in having a curing of free radical, with easily being produced because of oxygen The problem of solidification of raw solidification obstruction therefore the near interface of coating agent and air easily becomes insufficient.

In addition, also report has with the compound with the cation-curable such as hydrolyzable silyl group or epoxy radicals functional group The coating agent (patent document 2,3) solidified for main constituent, using photoacid generator.Make with water-disintegrable first silicon When the compound of the cation-curable such as alkyl or epoxy radicals functional group carries out photocuring for the solidification compound of principal component, no Solidification is hindered because of the oxygen in air, whole film is instantaneously solidified, and shows sufficient hardness, marresistance.

Wherein, high rigidity, height are easily shown by siloxanes key formed by the cationic curing of hydrolyzable silyl group Marresistance, therefore, receives much concern.But, when being solidified using hydrolyzable silyl group, with hydrolysis, condensation polymerization Carry out cure shrinkage, the generation in crack or the generation of warpage as it is big the problem of produce.Therefore widely carry out using with ring The silane compound of epoxide or vinyl etc. makes its hydrolyzable silyl group be entered in advance with the acid catalyst such as hydrochloric acid or acetic acid, formic acid Water-filling solution, condensation polymerization, the trial of photocuring is carried out using epoxy radicals or vinyl etc..Wherein, from consolidating after suppression photocuring Change from the viewpoint of shrinking, commonly using epoxy radicals, but there are the following problems：Because epoxy radicals is water-disintegrable, therefore, above-mentioned It is hydrolyzed under acid catalyst, it is impossible to obtain sufficient Physical properties of coating film.Considering to full panels such as smart mobile phone or tablet personal computers Application when, it is necessary to which film has excellent hardness, marresistance, in order to obtain high crosslink density, it is necessary to remain ring as far as possible Epoxide.

In addition, there are the following problems for the layered product with the layer being made up of polyfunctional acrylic ester system solidification compound： When being placed under the conditions of hot and humid, warpage is produced.

Prior art literature

Patent document

Patent document 1:Japanese Unexamined Patent Publication 5-230397 publications

Patent document 2:Japanese Unexamined Patent Publication 2000-109695 publications

Patent document 3:Japanese Unexamined Patent Publication 2004-204228 publications

The content of the invention

Invent problem to be solved

The problem to be solved by the present invention is that there is provided a kind of hardness, marresistance, excellent impact resistance, not producing solidification The solidification compound in crack caused by shrinking.

Technical scheme for solving problem

The present invention relates to a kind of active energy ray-curable composition, it is characterised in that is represented containing following logical formula (I)s are made , the silane compound (I) with hydrolyzable silyl group and following logical formula (II)s are represented, with hydrolyzable silyl group Silane compound (II), the mol ratio by silane compound (II) relative to silane compound (I) is set to less than 2.0 and in alkali Be hydrolyzed under the conditions of property, be condensed obtained from weight average molecular weight 20, less than 000 condensation product (A) and photoacid generator (B),

R¹-(SiR² _a(OR³)_3-a) (I)

(in formula, R¹The alkyl for the carbon number 1~10 that be instead of for end by 3,4- epoxycyclohexyls, R²Separately For the aralkyl of the alkyl selected from hydrogen atom or carbon number 1~10, the aryl of carbon number 6~25 and carbon number 7~12 In 1 valency alkyl, R³It is separately hydrogen atom or the alkyl of carbon number 1~10.A is 0~2 integer.)

R⁴-Si(OR³)₃ (II)

(in formula, R⁴Substituted or unsubstituted alkyl, alkenyl and substituted aryl selected from carbon number 1~10, and For the group without 3,4- epoxycyclohexyls, R³It is separately hydrogen atom or the alkyl of carbon number 1~10.)

The OR for the silicon atom Direct Bonding having with condensation product (A)³The molal quantity Y of base is relative to being used as condensation product (A) Raw material silane compound (I) and the OR of silicon atom Direct Bonding that has of silane compound (II)³The ratio between molal quantity X of base Y/X is less than 0.2.

R¹Preferably β-(3,4- epoxycyclohexyls) ethyl.

Condensation product (A) be preferably use as silane compound (II) following formulas (II-1) represent, with hydrolysis Property silicyl silane compound (II-1) and following formulas (II-2) represent, silane with hydrolyzable silyl group Compound (II-2), is set to 0.03~1.0, by silicon by silane compound (II-1) relative to the mol ratio of silane compound (I) Hydride compounds (II-2) are set to 0~1.0 to be hydrolyzed relative to the mol ratio of silane compound (I), be condensed obtained from,

R⁵-Si(OR³)₃ (II-1)

(in formula, R⁵The carbon number 1~10 that instead of selected from (methyl) acryloyl group, glycidyl or by mercapto Alkyl, the alkenyl and substituted aryl of carbon number 2~10, for the group without 3,4- epoxycyclohexyls, R³Respectively It independently is the alkyl of hydrogen atom or carbon number 1~10.)

R⁶-Si(OR³)₃ (II-2)

(in formula, R⁶Selected from amino, phenyl, cyclohexyl or, the alkyl and carbon of the carbon number 1~10 that are replaced by chlorine The unsubstituted alkyl of atomicity 1~10, for the group without 3,4- epoxycyclohexyls, R³It is separately hydrogen atom or carbon The alkyl of atomicity 1~10.).

Active energy ray-curable composition preferably also contains cycloaliphatic epoxy (D).

Cycloaliphatic epoxy (D) is preferably 3,4- epoxycyclohexyl-methyls -3 ', 4 '-epoxycyclohexane carboxylate.

Active energy ray-curable composition is preferably also containing the metal oxide microparticle that average grain diameter is below 100nm (E)。

Metal oxide microparticle (E) is preferably silicon dioxide microparticle.

Active energy ray-curable composition preferably with respect to the parts by weight of condensation product (A) 100, contain photoacid generator (B) 0.05~30 parts by weight, the parts by weight of cycloaliphatic epoxy (D) 0~100 and the weight of metal oxide microparticle (E) 0~100 Part.

Photoacid generator (B) is preferably aromatic series sulfonium salt or aromatic iodonium salts.

The counter anion of photoacid generator (B) is preferably fluorophosphoric acid ester series anion or fluorine metaantimmonic acid ester series anion.

Active energy ray-curable composition preferably also contains photosensitizer (F).

Photosensitizer (F) is preferably anthracene derivant, thioxanthone derivates or benzophenone derivates.

The invention further relates to a kind of solidfied material, it makes the active energy ray-curable composition solidification of the present invention and obtained.

The invention further relates to a kind of manufacture method of layered product, it is included：By the active energy ray-curable group of the present invention The process and irradiation active energy ray that compound is coated on base material make active energy ray-curable composition be solidified to form solidification to cover The process of film.

The invention further relates to a kind of layered product, it is obtained by above-mentioned manufacture method.

Preferably use as silane compound (II) following formulas (II-1) expression, with hydrolyzable silyl group Silane compound (II-1) and following formulas (II-2) represent, silane compound (II- with hydrolyzable silyl group 2) silane compound (II-1), is set to 0.03~1.0 relative to the mol ratio of silane compound (I), by silane compound (II-2) mol ratio relative to silane compound (I) be set to 0~1.0 to be hydrolyzed, be condensed obtained from condensation product (A) work Property energy ray-curable composition and the layered product manufactured using single layer of substrate material,

R⁵-Si(OR³)₃ (II-1)

(in formula, R⁵Selected from (methyl) acryloyl group, glycidyl or, the carbon number 1 that instead of by mercapto~ 10 alkyl, the alkenyl and substituted aryl of carbon number 2~10, for the group without 3,4- epoxycyclohexyls, R³Point The alkyl of hydrogen atom or carbon number 1~10 independently is not.)

R⁶-Si(OR³)₃ (II-2)

(in formula, R⁶Selected from amino, phenyl, cyclohexyl or, the alkyl and carbon of the carbon number 1~10 that are replaced by chlorine The unsubstituted alkyl of atomicity 1~10, be the group without 3,4- epoxycyclohexyls, R³It is separately hydrogen atom or carbon The alkyl of atomicity 1~10.).

The effect of invention

According to the present invention it is possible to provide hardness, marresistance, excellent impact resistance, not produce and split caused by cure shrinkage The solidification compound of seam.

Embodiment

Hereinafter, the details of the present invention is described.

The active energy ray-curable composition of the present invention is characterised by, containing making the silicon with hydrolyzable silyl group Hydride compounds (I) and silane compound (II) with hydrolyzable silyl group are in silane compound (II) relative to silane chemical combination The mol ratio of thing (I) turn into less than 2.0 under conditions of, be hydrolyzed in the basic conditions, be condensed obtained from weight average molecular weight Less than 20,000 condensation product (A) and photoacid generator (B), the OR for the silicon atom Direct Bonding having with condensation product (A)³Base rubs Your number Y is straight relative to the silicon atom that the silane compound (I) and silane compound (II) with the raw material as condensation product (A) have Meet the OR of bonding³The ratio between the molal quantity X of base Y/X is less than 0.2.

＜ (A) condensation products ＞

Silane compound (I) with hydrolyzable silyl group is with following logical formula (I)s：

R¹-(SiR² _a(OR³)_3-a) (I)

(in formula, R¹The alkyl for the carbon number 1~10 that be instead of for end by 3,4- epoxycyclohexyls, R²Separately For the aralkyl of the alkyl selected from hydrogen atom or carbon number 1~10, the aryl of carbon number 6~25 and carbon number 7~12 In 1 valency alkyl, R³It is separately hydrogen atom or the alkyl of carbon number 1~10.A is 0~2 integer.) represent.

Silane compound (II) with hydrolyzable silyl group is with following logical formula (II)s：

R⁴-Si(OR³)₃ (II)

(in formula, R⁴Substituted or unsubstituted alkyl, alkenyl and substituted aryl selected from carbon number 1~10, be Group without 3,4- epoxycyclohexyls, R³It is separately hydrogen atom or the alkyl of carbon number 1~10.) represent.

The R of logical formula (I)¹The alkyl for the carbon number 1~10 that be instead of for end by 3,4- epoxycyclohexyls, can enumerate example Such as：(3,4- epoxycyclohexyls) methyl, (3,4- epoxycyclohexyls) ethyl, (3,4- epoxycyclohexyls) propyl group, (3,4- epoxide rings Hexyl) butyl, (3,4- epoxycyclohexyls) amyl group and (3,4- epoxycyclohexyls) hexyl.

The R of logical formula (I)²For the alkyl selected from hydrogen atom or carbon number 1~10, the aryl and carbon of carbon number 6~25 The alkyl of 1 valency in the aralkyl of atomicity 7~12.As such alkyl, it can enumerate for example：Methyl, ethyl, propyl group, fourth Base, amyl group, hexyl, octyl group, nonyl, decyl, phenyl, tolyl, xylyl, naphthyl, benzyl and phenethyl.

The R of logical formula (I) and (II)³For hydrogen atom or the alkyl of carbon number 1~10.As alkyl, it can enumerate for example：First Base, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, nonyl and, decyl.From easily making the silicon with hydrolyzable silyl group From the viewpoint of hydride compounds hydrolysis, condensation, preferably R³Alkyl carbon number be 1~3, most preferably 1.

The R of logical formula (II)⁴Substituted or unsubstituted alkyl, alkenyl and substitution virtue selected from carbon number 1~10 Base, for the group without 3,4- epoxycyclohexyls.As alkyl, it can enumerate for example：Methyl, ethyl, propyl group, butyl, amyl group, Hexyl, octyl group, nonyl and, decyl.As the substituent of alkyl, it can enumerate：Glycidyl, mercapto, amino, (methyl) Acryloyl group, phenyl, cyclohexyl and chloro.As alkenyl, it can enumerate for example：Vinyl, pi-allyl, 3- cyclobutenyls, 4- penta Alkenyl, 5- hexenyls, 6- heptenyls, 7- octenyls.As substituted aryl, styryl can be enumerated.

Wherein, from storage-stable is good, active energy ray irradiation when curing rate it is fast and then can suppress what is obtained From the aspect of the crack of film is produced, R is used as⁴, when it is unsubstituted alkyl, preferably carbon number is below more than 3 10 Alkyl, more preferably alkyl of the carbon number below more than 36.Its for substitution alkyl when, preferably the carbon number of alkyl be 3 with Upper less than 10, more preferably carbon number is less than more than 36, the preferred phenyl of substituent, cyclohexyl and (methyl) acryloyl group.Its During for alkenyl, preferred vinyl or pi-allyl.It is used as substituted aryl, optimization styrene base.Carbon number in unsubstituted alkyl For less than 2 when or substitution alkyl in substituent unlike phenyl, cyclohexyl or big (methyl) acryloyl group volume when, sometimes hand over As fine and close cross-linked structure during connection, gelation is carried out.In addition, when the carbon number of alkyl is more than 11 or in substitution alkyl When substituent is unlike phenyl, cyclohexyl or also big (methyl) acryloyl group volume, hydrophobicity is raised sometimes, and hydrolysis rate is extreme Reduction, or curing rate reduction during active energy ray irradiation.

The a of logical formula (I) is 0~2 integer, the physical property according to required by solidification compound and suitably select.

As silane compound (I), it can enumerate：α-(3,4- epoxycyclohexyls) MTMS, α-(3,4- rings Oxygen cyclohexyl) methyl dimethoxysilane, α-(3,4- epoxycyclohexyls) methyl dimethoxy methoxylsilane, α-(3,4- Epoxycyclohexyl) MTES, α-(3,4- epoxycyclohexyls) methyl diethoxy silane, α-(3,4- rings Oxygen cyclohexyl) methyl dimethoxy base oxethyl silane, α-(3,4- epoxycyclohexyls) methyl tripropoxy silane, α-(3,4- epoxies Cyclohexyl) α-(the 3,4- rings such as methyl dipropoxy silane, α-(3,4- epoxycyclohexyls) methyl dimethoxy base npropoxysilane Oxygen cyclohexyl) methyl-monosilane class, β-(3,4- epoxycyclohexyls) ethyl trimethoxy silane, β-(3,4- epoxycyclohexyls) ethyl Methyl dimethoxysilane, β-(3,4- epoxycyclohexyls) ethyl dimethyl methoxy silane, β-(3,4- epoxycyclohexyls) second Ethyl triethoxy silicane alkane, β-(3,4- epoxycyclohexyls) ethyl-methyl diethoxy silane, β-(3,4- epoxycyclohexyls) ethyl Dimethylethoxysilane, β-(3,4- epoxycyclohexyls) ethyl tripropoxy silane, β-(3,4- epoxycyclohexyls) ethyl first The β such as base dipropoxy silane, β-(3,4- epoxycyclohexyls) ethyl dimethyl propylene TMOS-(3,4- epoxycyclohexyls) ethyl Silanes, γ-(3,4- epoxycyclohexyls) propyl trimethoxy silicane, γ-(3,4- epoxycyclohexyls) hydroxypropyl methyl dimethoxy Base silane, γ-(3,4- epoxycyclohexyls) dimethylamine methoxylsilane, γ-ethoxy of (3,4- epoxycyclohexyls) propyl group three Base silane, γ-(3,4- epoxycyclohexyls) hydroxypropyl methyl diethoxy silane, γ-(3,4- epoxycyclohexyls) propyl-dimethyl Ethoxysilane, γ-(3,4- epoxycyclohexyls) propyl group tripropoxy silane, γ-(3,4- epoxycyclohexyls) hydroxypropyl methyl two The γ such as npropoxysilane, γ-(3,4- epoxycyclohexyls) propyl-dimethyl npropoxysilane-(3,4- epoxycyclohexyls) propyl group silicon Alkanes, δ-(3,4- epoxycyclohexyls) butyl trimethoxy silane, δ-(3,4- epoxycyclohexyls) butyl methyl dimethoxy silicon Alkane, δ-(3,4- epoxycyclohexyls) Butyldimethyl methoxy silane, δ-(3,4- epoxycyclohexyls) butyl triethoxysilane, δ-(3,4- epoxycyclohexyls) butyl methyl diethoxy silane, δ-(3,4- epoxycyclohexyls) Butyldimethyl ethyoxyl silicon Alkane, δ-(3,4- epoxycyclohexyls) butyl tripropoxy silane, δ-(3,4- epoxycyclohexyls) butyl methyl dipropoxy silane, The δ such as δ-(3,4- epoxycyclohexyls) Butyldimethyl npropoxysilane-(3,4- epoxycyclohexyls) butylsilane class, ε-(3,4- Epoxycyclohexyl) amyltrimethoxysilane, ε-(3,4- epoxycyclohexyls) phenyl-methyl dimethoxysilane, ε-(3,4- rings Oxygen cyclohexyl) amyl dimethyl methoxy silane, ε-(3,4- epoxycyclohexyls) amyl triethoxysilane, ε-(3,4- epoxies Cyclohexyl) phenyl-methyl diethoxy silane, ε-(3,4- epoxycyclohexyls) amyl dimethyl Ethoxysilane, ε-(3,4- rings Oxygen cyclohexyl) amyl group tripropoxy silane, ε-(3,4- epoxycyclohexyls) phenyl-methyl dipropoxy silane, ε-(3,4- epoxies Cyclohexyl) ε-(3,4- epoxycyclohexyls) pentylsilane class, ζ-(the 3,4- epoxycyclohexyls) such as amyl dimethyl npropoxysilane Hexyl trimethoxy silane, ζ-(3,4- epoxycyclohexyls) hexyl methyl dimethoxysilane, ζ-(3,4- epoxycyclohexyls) oneself Base dimethyl methoxy silane, ζ-(3,4- epoxycyclohexyls) hexyl triethoxysilane, ζ-(3,4- epoxycyclohexyls) hexyl Methyldiethoxysilane, ζ-(3,4- epoxycyclohexyls) hexyl dimethylethoxysilane, ζ-(3,4- epoxycyclohexyls) oneself Base tripropoxy silane, ζ-(3,4- epoxycyclohexyls) hexyl methyl dipropoxy silane, ζ-(3,4- epoxycyclohexyls) hexyl The ζ such as dimethyl propylene TMOS-(3,4- epoxycyclohexyls) hexyl silane class, η-(3,4- epoxycyclohexyls) heptyl trimethoxy Silane, η-(3,4- epoxycyclohexyls) hept-ylmethyl dimethoxysilane, η-(3,4- epoxycyclohexyls) heptyl dimethyl methoxy Base silane, η-(3,4- epoxycyclohexyls) heptyl triethoxysilane, η-(3,4- epoxycyclohexyls) hept-ylmethyl diethoxy Silane, η-(3,4- epoxycyclohexyls) heptyl dimethylethoxysilane, η-(3,4- epoxycyclohexyls) heptyl tripropoxy silicon Alkane, η-(3,4- epoxycyclohexyls) hept-ylmethyl dipropoxy silane, η-(3,4- epoxycyclohexyls) heptyl dimethyl propylene epoxide The η such as silane-(3,4- epoxycyclohexyls) heptyl silanes, θ-(3,4- epoxycyclohexyls) octyl group trimethoxy silane, θ-(3,4- Epoxycyclohexyl) octyl methyl dimethoxysilane, θ-(3,4- epoxycyclohexyls) octyldimethyl methoxy silane, θ-(3, 4- epoxycyclohexyls) octyltri-ethoxysilane, θ-(3,4- epoxycyclohexyls) octyl methyl diethoxy silane, θ-(3,4- Epoxycyclohexyl) octyldimethyl Ethoxysilane, θ-(3,4- epoxycyclohexyls) octyl group tripropoxy silane, θ-(3,4- rings Oxygen cyclohexyl) the θ-(3,4- such as octyl methyl dipropoxy silane, θ-(3,4- epoxycyclohexyls) octyldimethyl npropoxysilane Epoxycyclohexyl) octyl group silanes.

As described above, from the viewpoint of the silane compound hydrolysis, condensation easily made with hydrolyzable silyl group, it is excellent R in gating formula (I)³Alkyl carbon number be 1~3, most preferably 1.In addition, from active energy ray irradiate when epoxy From the viewpoint of the reactivity of cyclohexyl, the carbon number for the alkylidene that epoxycyclohexyl is bonded with silicon atom is important , its carbon number preferably 1~4, more preferably 2 or 3.Above-mentioned viewpoint is combined, as silane compound (I), It is preferred that β-(3,4- epoxycyclohexyls) ethyl trimethoxy silane, β-(3,4- epoxycyclohexyls) ethyl-methyl dimethoxy silicon Alkane, β-(3,4- epoxycyclohexyls) ethyl dimethyl methoxy silane, γ-(3,4- epoxycyclohexyls) propyl trimethoxy silicon Alkane, γ-(3,4- epoxycyclohexyls) hydroxypropyl methyl dimethoxysilane and γ-(3,4- epoxycyclohexyls) propyl-dimethyl first TMOS.Wherein, preferably R¹For the compound of β-(3,4- epoxycyclohexyls) ethyl.

In silane compound (II), the R in logical formula (II) is used as⁴For the compound of unsubstituted alkyl, it can enumerate：First Base trimethoxy silane, MTES, methyl tripropoxy silane, ethyl trimethoxy silane, the ethoxy of ethyl three Base silane, ethyl tripropoxy silane, propyl trimethoxy silicane, propyl-triethoxysilicane, propyl group tripropoxy silane, fourth Base trimethoxy silane, butyl triethoxysilane, butyl tripropoxy silane, amyltrimethoxysilane, the ethoxy of amyl group three Base silane, amyl group tripropoxy silane, hexyl trimethoxy silane, hexyl triethoxysilane, hexyl tripropoxy silane, heptan Base trimethoxy silane, heptyl triethoxysilane, heptyl tripropoxy silane, octyl group trimethoxy silane, the ethoxy of octyl group three Base silane, octyl group tripropoxy silane, nonyl trimethoxy silane, nonyl triethoxysilane, nonyl tripropoxy silane, the last of the ten Heavenly stems Base trimethoxy silane, decyl triethoxysilane, decyl tripropoxy silane etc..

In addition, being used as the R in logical formula (II)⁴To replace the compound of alkyl, following compounds can be enumerated.Here, making For substituent, it is not particularly limited, from the viewpoint of easy degree is obtained, preferably glycidyl, mercapto, amino, (first Base) acryloyl group, phenyl, cyclohexyl and chloro.

It is used as R⁴Replace the compound of alkyl for glycidyl, can enumerate：Glycidyl oxy methyl trimethoxy silane, Glycidyl oxy methyl triethoxysilane, 2- glycidoxyethyls trimethoxy silane, the second of 2- glycidoxyethyls three TMOS, 3- glycidoxypropyltrime,hoxysilanes, 3- glycidoxypropyl groups triethoxysilane, the oxygen of 4- epoxies third Base butyl trimethoxy silane, 4- glycidoxy butyl triethoxysilane, 5- glycidoxies amyltrimethoxysilane, 5- glycidoxies amyl triethoxysilane, 6- glycidoxy hexyls trimethoxy silane, 6- glycidoxies hexyl three Ethoxysilane etc..

It is used as R⁴Replace the compound of alkyl for mercapto, can enumerate：Mercapto methyl trimethoxy silane, mercapto methyl three Ethoxysilane, 2- mercaptoethyls trimethoxy silane, 2- mercaptoethyls triethoxysilane, 3- mercaptopropyi trimethoxy silicon Alkane, 3- Mercaptopropyltriethoxysilanes, 4- mercaptobutyls trimethoxy silane, 4- mercaptobutyls triethoxysilane, 5- mercaptos Base amyltrimethoxysilane, 5- sulfydryls amyl triethoxysilane, 6- sulfydryl hexyls trimethoxy silane, 6- sulfydryls hexyl three Ethoxysilane etc..

It is used as R⁴Replace the compound of alkyl for amino, can enumerate：N-2- (amino-ethyl) amino methyl trimethoxy silicon Alkane, N-2- (amino-ethyl) amino methyls triethoxysilane, N-2- (amino-ethyl) -2- amino-ethyls trimethoxy silane, N-2- (amino-ethyl) -2- amino-ethyls triethoxysilane, N-2- (amino-ethyl) -3- TSL 8330s, N-2- (amino-ethyl)-APTES, N-2- (amino-ethyl) -4- aminobutyls trimethoxy silane, N-2- (amino-ethyl) -4- ammobutyltriethoxysilanes, N-2- (amino-ethyl) -5- Aminopentyls trimethoxy silane, N-2- (amino-ethyl) -5- Aminopentyls triethoxysilane, N-2- (amino-ethyl) -6- Aminohexyls trimethoxy silane, N-2- (amino-ethyl) -6- Aminohexyls triethoxysilane, amino methyl trimethoxy silane, amino methyl triethoxysilicane Alkane, 2- amino-ethyls trimethoxy silane, 2- amino-ethyls triethoxysilane, 3- TSL 8330s, 3- ammonia Base propyl-triethoxysilicane, 4- aminobutyls trimethoxy silane, 4- ammobutyltriethoxysilanes, 5- Aminopentyls three Methoxy silane, 5- Aminopentyls triethoxysilane, 6- Aminohexyls trimethoxy silane, 6- Aminohexyl triethoxysilicanes Alkane, N- phenvlaminomethvls trimethoxy silane, N- phenvlaminomethvls triethoxysilane, N- phenyl -2- amino-ethyls three Methoxy silane, N- phenyl -2- amino-ethyls triethoxysilane, N- phenyl -3- TSL 8330s, N- benzene Base-APTES, N- phenyl -4- aminobutyls trimethoxy silane, the second of N- phenyl -4- aminobutyls three TMOS, N- phenyl -5- Aminopentyls trimethoxy silane, N- phenyl -5- Aminopentyls triethoxysilane, N- phenyl - 6- Aminohexyls trimethoxy silane, N- phenyl -6- Aminohexyl triethoxysilanes etc..

It is used as R⁴Replace the compound of alkyl for (methyl) acryloyl group, can enumerate：(methyl) acryloyloxymethyl three Methoxy silane, (methyl) acryloyloxymethyl triethoxysilane, 2- (methyl) acryloyl-oxyethyl trimethoxy silicon Alkane, 2- (methyl) acryloyl-oxyethyls triethoxysilane, 3- (methyl) acryloxypropyls trimethoxy silane, 3- (methyl) acryloxypropyl triethoxysilane, 4- (methyl) acryloxies butyl trimethoxy silane, 4- (methyl) Acryloxy butyl triethoxysilane, 5- (methyl) acryloxies amyltrimethoxysilane, 5- (methyl) acryloyl Epoxide amyl triethoxysilane, 6- (methyl) acryloxy hexyl trimethoxy silane, 6- (methyl) acryloxy oneself Ethyl triethoxy silicane alkane etc..

It is used as R⁴For the compound of phenyl substituted alkyl, it can enumerate：Benzyl trimethoxy silane, benzyl triethoxysilicane Alkane, 2- phenylethyls trimethoxy silane, 2- phenylethyls triethoxysilane, 3- phenyl propyls trimethoxy silane, 3- benzene Base propyl-triethoxysilicane, 4- phenyl butyls trimethoxy silane, 4- phenyl butyls triethoxysilane, 5- phenylpentyls three Methoxy silane, 5- phenylpentyls triethoxysilane, 6- Phenylhexyls trimethoxy silane, 6- Phenylhexyl triethoxysilicanes Alkane etc..

It is used as R⁴Replace the compound of alkyl for cyclohexyl, can enumerate：Cyclohexyl methyl trimethoxy silane, cyclohexyl first Ethyl triethoxy silicane alkane, 2- cyclohexyl-ethyls trimethoxy silane, 2- cyclohexyl-ethyls triethoxysilane, 3- Cyclohexylpropyls Trimethoxy silane, 3- Cyclohexylpropyls triethoxysilane, 4- cyclohexylbutyls trimethoxy silane, 4- cyclohexylbutyls three Ethoxysilane, 5- cyclohexylpentyls trimethoxy silane, 5- cyclohexylpentyls triethoxysilane, 6- cyclohexylhexyl front threes TMOS, 6- cyclohexylhexyl triethoxysilanes etc..

It is used as R⁴Replace the compound of alkyl for chloro, can enumerate for example：Chloromethyl trimethoxy silane, the second of chloromethyl three TMOS, 2- chloroethyls trimethoxy silane, 2- chloroethyls triethoxysilane, 3- r-chloropropyl trimethoxyl silanes, 3- chlorine Propyl-triethoxysilicane, 4- chlorobutyls trimethoxy silane, 4- chlorobutyl triethoxy silanes, 5- chlorine amyl group trimethoxy silicon Alkane, 5- chlorine amyl triethoxysilane, 6- chlorine hexyls trimethoxy silane, 6- chlorine hexyl triethoxysilanes etc..

It is used as R⁴For the compound of alkenyl, it can enumerate for example：Vinyltrimethoxy silane, vinyl triethoxyl silicon Alkane, allyltrimethoxysilanis, allyltriethoxysilane, 3- cyclobutenyls trimethoxy silane, the ethoxy of 3- cyclobutenyls three Base silane, 4- pentenyls trimethoxy silane, 4- pentenyls triethoxysilane, 5- hexenyls trimethoxy silane, 5- hexenes Ethyl triethoxy silicane alkane, 6- heptenyls trimethoxy silane, 6- heptenyls triethoxysilane, 7- octenyl trimethoxy silicon Alkane, 7- octenyltriethoxysilanes etc..

It is used as R⁴For the compound of substituted aryl, it can enumerate：To styryl trimethoxy silane, to the second of styryl three TMOS etc..

There are many 3,4- epoxycyclohexyls in condensation product (A) preferably 1 molecule.From friendship when improving the irradiation of energy active line Join from the viewpoint of density, the physical property of raising solidfied material, the number of 3, the 4- epoxycyclohexyls in 1 molecule is preferably more than 4, More preferably more than 5, further preferred more than 6.The number of 3,4- epoxycyclohexyls in 1 molecule is more, and condensation body (A) is got over For HMW body.Condensation body (A) more carries out molecular weight, and intermolecular cross-linking during as to solidification is not contributed and produced Intramolecular crosslinking or the possibility for being not involved in being crosslinked and being buried in the functional group of intramolecular completely are higher, therefore, in 1 molecule The number of 3,4- epoxycyclohexyls is preferably less than 100, more preferably less than 90, more preferably less than 80, enters one Step more preferably less than 70, particularly preferred less than 60.

Condensation product (A) is in mol ratio (silane compound (II) of the silane compound (II) relative to silane compound (I) Molal quantity/silane compound (I) molal quantity) turn into less than more than 0 2.0 under conditions of be hydrolyzed, be condensed obtained from. When mol ratio is more than 2.0, the effect of warpage becomes caused by cure shrinkage when suppressing to be formed the layered product relative to single layer of substrate material Obtain insufficient.In addition, when the content of 3, the 4- epoxycyclohexyls in condensation product (A) is reduced, intermolecular cross-linking becomes insufficient, load Hard-hearted degree or marresistance reduction, accordingly, it is considered to which during hard painting propert (i.e. hardness or marresistance), mol ratio is preferably more than 0 1.0 Hereinafter, more preferably less than more than 0 0.8, more preferably less than more than 0 0.6, particularly preferably less than more than 0 0.4, most Preferably less than more than 0 0.2.

The weight average molecular weight of condensation product (A) is less than 20,000.Weight average molecular weight is preferably more than 500, and more preferably 1,000 More than, further preferred 1, more than 500, even more preferably 2, more than 000, particularly preferred 2, more than 800.In addition, divide equally again Son amount more preferably 18, less than 000, further preferred 16, less than 000, even more preferably 14, less than 000, particularly preferably Less than 12,000.The weight average molecular weight of condensation product (A) be less than 500 when, it is possible to have volatility, before curing part or all Volatilization.In addition, worrying that weight average molecular weight is lower, impact resistance is more reduced.When weight average molecular weight is more than 20,000, it is possible to it The intermiscibility reduction of its complex, the gonorrhoea when film is formed.It should be noted that weight average molecular weight is determined with GPC Weight average molecular weight.

The OR for the silicon atom Direct Bonding having with condensation product (A)³The molal quantity Y of base is relative to being used as condensation product (A) Raw material silane compound (I) and the OR of silicon atom Direct Bonding that has of silane compound (II)³The ratio between molal quantity X of base Y/X is less than 0.2.When Y/X is more than 0.2, after active energy ray irradiation film through when shrink and produce crack.Y/X is more excellent Less than 0.1, even more preferably less than 0.05 is selected, is most preferably essentially 0.

Y/X can be by using¹HNMR is measured and obtained.

In addition, the amount of the water required in hydrolysis, condensation reaction is relative to the OR with silicon atom Direct Bonding³Base is 0.3 ~3 equivalents, preferably 0.5~2 equivalent.When the amount of water is less than 0.3 equivalent, OR sometimes³A part for base is not hydrolyzed and remaining.When When it is more than 3 equivalent, hydrolysis sometimes, condensation reaction speed it is excessive and generate the condensation product of HMW, make film physical property, Transparency reduction.

The OR remained in condensation product (A)³It is less than 2 in the number of base preferably 1 molecule, more preferably less than 1, enters One step is more preferably less than 0.5, particularly preferably less than 0.1, most preferably substantially not remaining.

From the viewpoint of improving crosslink density and improving the hardness or marresistance of solidfied material, preferred condensation product (A) In 3,4- epoxycyclohexyls survival rate, i.e. condensation product (A) in 3,4- epoxycyclohexyls molal quantity relative to being used as original The ratio of the molal quantity for the 3,4- epoxycyclohexyls that the silane compound (I) of material has is high.It is used as the residual of 3,4- epoxycyclohexyls Rate is deposited, specifically, preferably more than 20%, more preferably more than 40%, more preferably more than 60%.3,4- epoxide rings The survival rate of hexyl can pass through¹HNMR is determined and obtained.

In addition, hydrolysis, condensation reaction are implemented in the basic conditions.Alicyclic epoxy thing and fat as epoxycyclohexyl Fat race epoxides is compared, and reactivity is big different, and electrophilic reaction is easily carried out, and asks nuclear reaction to be difficult to, therefore, in acid Property under the conditions of the easy open loop of epoxy radicals, on the other hand, open loop can be suppressed in the basic conditions.Therefore, close in the basic conditions Into condensation product a side, epoxy radicals survival rate is high, the film of high crosslink density can be obtained, therefore, in hardness, marresistance In terms of preferably.PH in hydrolysis, condensation reaction is 7~14, from the viewpoint of reaction speed, preferably 8~14.pH It can be measured using glass electrode method.

As for by reaction system be set to alkalescence alkali compounds, be not particularly limited, can use sodium hydroxide, Amines such as the hydroxide or triethylamine of the alkali metal such as lithium hydroxide, magnesium hydroxide or alkaline-earth metal etc..Synthetic condensation agent thing Afterwards, made using photoacid generator epoxy curing, it is therefore preferable that alkali compounds is easily removed, from this viewpoint, preferably volatilized Property it is high.And then, nucleophilicity is it is also preferred that low, and therefore, as alkali compounds, preferred tertiary amine compound, it is considered to during applicability is more excellent Select the tertiary amine compound that boiling point is 30 DEG C~160 DEG C.Specifically, it can enumerate：Triethylamine, diethylmethyl amine, tripropyl Amine, methyl diisopropylamine and diisopropyl ethyl amine.

From the viewpoint of the generation of warpage from single layer of substrate material is suppressed, the silanization of formula (II-1) expression is preferably used Compound (II-1), the raw material as needed for also using the silane compound (II-2) that formula (II-2) is represented as condensation product (A) The silane compound (II) with hydrolyzable silyl group, by silane compound (II-1) relative to silane compound (I) Mol ratio, which is set to 0.03~1.0, silane compound (II-2) is set into 0~1.0 relative to the mol ratio of silane compound (I) enters Water-filling solution, condensation.

Silane compound (II-1) with hydrolyzable silyl group is with following formulas (II-1)：

R⁵-Si(OR³)₃ (II-1)

(in formula, R⁵Selected from (methyl) acryloyl group, glycidyl or, the carbon number 1 that instead of by mercapto~ 10 alkyl, the alkenyl and substituted aryl of carbon number 2~10, for the group without 3,4- epoxycyclohexyls, R³Point The alkyl of hydrogen atom or carbon number 1~10 independently is not.) represent.

Silane compound (II-2) with hydrolyzable silyl group is with following formulas (II-2)：

R⁶-Si(OR³)₃ (II-2)

(in formula, R⁶Selected from amino, phenyl, cyclohexyl or, the alkyl and carbon of the carbon number 1~10 that are replaced by chlorine The unsubstituted alkyl of atomicity 1~10, for the group without 3,4- epoxycyclohexyls, R³It is separately hydrogen atom or carbon The alkyl of atomicity 1~10.) represent.

From the viewpoint of the generation of warpage from the layered product relative to single layer of substrate material is suppressed, silane compound (I) can To be caught as expanded constituents during solidification, silane compound (II-1) can be caught as contractile element during solidification, be passed through The balance of expanded constituents and contractile element is obtained, the warpage due to cure shrinkage can be suppressed.Silane compound (II-1) phase For silane compound (I) mol ratio be more preferably more than 0.05, further preferred more than 0.075, particularly preferred 0.1 with On.In addition, mol ratio more preferably less than 0.9, further preferred less than 0.8, particularly preferred less than 0.6.Mol ratio is less than 0.03 When, the warpage due to setting expansion can not be suppressed sometimes, when it is more than 1.0, hard painting propert (i.e. hardness or scratch resistance sometimes Property) reduction.

Silane compound (II-2) is not also captured as any one of expanded constituents contractile element during solidification, makees Worked for a kind of diluted composition, can further reduce the influence of expanded constituents and contractile element.Silane compound (II-2) Mol ratio relative to silane compound (I) is more preferably less than 0.8, more preferably less than 0.6, particularly preferably 0.5 Below.When mol ratio is more than 1.0, hard painting propert (i.e. hardness or marresistance) is reduced sometimes.

The concentration of condensation product (A) in the solidification compound of the present invention is higher, more can obtain the high film of hardness, therefore It is preferred that.As the present invention solidification compound in condensation product (A) solid component concentration, preferably more than 60 weight %, more It is preferred that more than 70 weight %, even more preferably more than 80 weight %, most preferably particularly preferred more than 90 weight %, 95 weight % More than.

＜ (B) photoacid generators ＞

It is the chemical combination by producing acid exposed to active energy ray as the photoacid generator of (B) composition in the present invention Thing, can be enumerated for example：The strong acid such as toluenesulfonic acid or tetrafluoride boron；The salts such as sulfonium salt, ammonium salt, phosphonium salts, salt compounded of iodine, selenium salt；Iron- Allene complex species；Silanol-metal-chelate complexes class；Two sulfone classes, the azomethane class of disulfonyl base two, disulfonyl base The sulfonic acids such as methane class, sulfonyl benzoyl methane class, acid imide sulfonic acid esters, benzoin sulfonic acid esters；Organic halogenation The compound that acid is produced by the irradiation of radioactive ray shown in the Japanese Unexamined Patent Publication 5-134412 publications such as compound class.

As sulfonic acid, it can enumerate for example：Benzoin toluene sulphur shown in No. 4618564 specifications of U.S. Patent No. The sulfonic acid esterses such as acid esters, nitrobenzyl tosylat, bromosuccinimide tosyl sulphonic acid ester；U.S. Patent No. α-(4- tosyloxies imino group) -4- methoxies shown in No. 4540598 specifications, Japanese Unexamined Patent Publication 6-67433 publications The oxime sulfonates classes such as base benzyl cyanine；Three (methanesulfonyloxy group) benzene shown in Japanese Unexamined Patent Publication 6-348015 publications etc.；Day 9,10- dialkoxy rylnthracene sulfonin nitrobenzyl esters shown in this JP 64-18143 publications etc.；N- is (to detergent alkylate sulphur Acyloxy) -1,8- naphthalimides etc..As organic halogenation compound species, it can enumerate for example：2- (4- methoxyphenyls) -4,6- is double Double (the trichloromethyl) -1,3,5- triazines of (trichloromethyl) -1,3,5- triazines, 2- (3,4 dimethoxy styrene base) -4,6-, 2- The Japanese Unexamined Patent Application 55-32070 such as double (the trichloromethyl) -1,3,5- triazines of [2- (5- methylfuran -2- bases) vinyl] -4,6- Publication, Japanese Unexamined Patent Application 48-36281 publications, the halogen triaizine compounds shown in Japanese Unexamined Patent Application 63-238339 publications； The halogen sulphones such as 2- pyridine radicals-trisbromomethyl sulfone shown in Japanese Unexamined Patent Publication 2-304059 publications；Three (2- chloropropyls) The halogenated alkyl phosphate esters such as phosphate, three (chloropropyls of 2,3- bis-) phosphates, three (2,3- dibromopropyls) phosphates；The chloro- 6- of 2- The halogen miscellaneous cyclic compound such as (trichloromethyl) pyridine；Double [the rubigan] -2,2,2- trichloroethanes of 1,1-, vinylidene chloride copolymerization Halogen hydrocarbon compounds such as thing, ethlyene dichloride base co-polymer, chloridized polyolefin etc..

In above-mentioned photoacid generator, from the condensation product (A) containing the silane compound with 3,4- epoxycyclohexyls Stability in composition is high and from the aspect of being readily available, optimization aromatic sulfonium salt or aromatic series iodineSalt.Wherein, from solid Change it is fast, excellent to the tack of plastic basis material from the aspect of, optimization aromatic sulfonium salt or aromatic series iodineThe counter anion of salt For fluorophosphoric acid ester series anion, fluorine metaantimmonic acid ester series anion or fluoboric acid ester series anion.Particularly preferred fluorophosphoric acid ester system it is cloudy from Son or fluorine metaantimmonic acid ester series anion.It is used as such photoacid generator, preferably diphenyl (4- phenylthiophenyls) sulfonium hexafluoro phosphorus Acid esters or diphenyl (4- phenylthiophenyls) sulfonium hexafluoro-antimonic acid ester.

The addition needs of photoacid generator (B) are adjusted according to sour yield, the generation speed of generation, relative to The parts by weight of condensation product (A) (solid constituent) 100, more preferably preferably 0.05~30 parts by weight, 0.1~10 parts by weight.Light is produced When the addition of sour agent (B) is less than 0.05 parts by weight, the subacidity that there is generation, the hardness of obtained film, marresistance are not Sufficiently tendency, when it is more than 30 parts by weight, there are problems that produce appearance of film reduction or tendency.

＜ (C) optical free radical producing agent ＞

Use silane compound (II-1), R⁵In contained group when showing reactivity because of optical free radical producing agent, it is excellent Match closing light free-radical generating agent.Optical free radical producing agent refers to the chemical combination by producing free radical exposed to active energy ray Thing, the R of silane compound (II-1)⁵In contained group when having free-radical polymerised, worked as polymerization initiator.

As optical free radical producing agent, it can enumerate：Carbonyls, sulphur compound, acylphosphine oxide etc..In more detail and Speech, can be enumerated for example：It is benzoin, benzoin monomethyl ether, benzoin isopropyl ether, 3-hydroxy-2-butanone, benzil, benzophenone, right Methoxy benzophenone, diethoxy acetophenone, benzyl dimethyl ketal, 2,2- diethoxy acetophenones, 1- hydroxy-cyclohexyls The carbonyl compounds such as phenyl ketone, methyl phenyl glyoxylate, ethylphenyl glyoxylate, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone The sulphur compounds such as thing, tetra methylthiuram list thioether, tetra methylthiuram disulfide, 2,4,6- trimethylbenzoyl dipheny oxides Change acylphosphine oxides such as phosphine etc..

The IRGACURE such as IRGACURE184 or IRGACURE819 series or DAROCUR1173 or DAROCUR TPO etc. The KAYACURE such as DAROCUR series (more than, BASF societies system), KAYACURE DETX-S, KAYACURE CTX series (more than, day This chemical drug society system), the TAZ such as TAZ-101, TAZ-110 series (more than, Green Chemistry society system) etc. is commercially available.

Optical free radical producing agent can be used alone, it is also contemplated that curing rate etc. and and with multiple.

Using addition needs during optical free radical producing agent according to yield, the target molecular weight of the free radical of generation It is adjusted, relative to the parts by weight of condensation product (A) 100, more than preferably 0.05 parts by weight, more than more preferably 0.1 parts by weight.Separately Outside, preferably below 50 parts by weight, below more preferably 30 parts by weight.The usage amount of optical free radical producing agent is less than 0.05 parts by weight When, the free radical that generates sometimes is not enough, is produced without solidification tacky, when it is more than 50 parts by weight, there is generation coloring Or tendency of weatherability the problems such as reduce.

＜ (D) cycloaliphatic epoxies ＞

The active energy line curing resin composition of the present invention can contain cycloaliphatic epoxy.It is used as ester ring type Epoxide, can enumerate such as 3,4- epoxycyclohexyl-methyls -3 ', 4 '-epoxycyclohexane carboxylate (such as Daicel Learn Industrial Co., Ltd's system：Trade name " CELLOXIDE2021P "), EPSILON- caprolactone modification 3,4- epoxycyclohexyl first Base -3 ', 4 '-epoxycyclohexane carboxylate (for example, Daisel chemical industry Co., Ltd's system：Trade name " CELLOXIDE2081 "), 1,2,8,9- diepoxies limonene (such as Daisel chemical industry Co., Ltd's system：Trade name " CELLOXIDE3000 "), vinylcyclohexene list oxide 1,2- epoxy -4- vinyl cyclohexanes (the chemical work of such as Daicel Industry Co. Ltd. system：Trade name " CELLOXIDE2000 "), 1,2- epoxies -4- (the 2- rings of double (the hydroxymethyl)-n-butyl alcohols of 2,2- Oxygen ethyl) hexamethylene addition product (such as Daisel chemical industry Co., Ltd's system：Trade name " EHPE-3150 "), double-(3,4- Epoxycyclohexyl) cycloaliphatic epoxy such as adipate ester, on annular aliphatic hydrocarbon directly or addition has ring via hydrocarbon The alicyclic epoxy things such as the epoxides containing heterocycle such as epoxide, the triglycidyl group isocyanuric acid ester of epoxide Deng.Wherein, the preferred epoxide with epoxycyclohexyl, more preferably as 3, the 4- epoxies of the liquid compound of low viscosity Cyclohexyl methyl -3 ', 4 '-epoxycyclohexane carboxylate.

(D) composition can be used as reactive diluent, can improve the masking liquid operability of active energy ray pre-irradiation. As the usage amount of (D) composition, relative to the parts by weight of (A) composition 100, preferably 0~100 parts by weight, more preferably 0~50 Parts by weight.(D) when the usage amount of composition is more than 100 parts by weight, it is possible to hardness or marresistance reduction.

＜ (E) metal oxide particles ＞

In the active energy ray-curable composition of the present invention, metal oxide microparticle can be used as needed.Make For the metal oxide microparticle of (E) composition, it can enumerate：Silica (SiO₂), aluminum oxide (Al₂O₃), tin oxide (SnO₂)、 Zirconium oxide (ZrO₂), zinc oxide (ZnO), titanium dioxide (TiO₂), ITO (tin indium oxide), antimony oxide (Sb₂O₃、Sb₂O₅) and they Composite particles etc..

Wherein, from the viewpoint of high rigidity, preferably silica, aluminum oxide, zirconium oxide and antimony oxide.Particularly from obtaining Consider in terms of the easy degree or cost, case hardness that obtain, preferably silicon dioxide microparticle and alumina particulate, particularly preferred two Silicon oxide particle.These materials can be used alone, or two or more is applied in combination.

Such metal oxide microparticle is preferably powder shaped or solvent dispersion sol.When it is solvent dispersion sol, from From the viewpoint of intermiscibility, dispersiveness with other compositions, decentralized medium preferable organic solvent.As such organic solvent, It can enumerate for example：The alcohols such as methanol, ethanol, isopropanol, butanol, octanol；Acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ring The ketones such as hexanone；The esters such as ethyl acetate, butyl acetate, ethyl lactate, δ-butyrolactone；Ethylene glycol single methyl ether, diethylene glycol The ethers such as monobutyl ether；Benzene,toluene,xylene etc. is aromatic hydrocarbon；Dimethylformamide, dimethyl acetamide, N- methylpyrroles The amide-types such as alkanone.Wherein, preferably alcohols, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethyl acetate, butyl acetate.

The average grain diameter (average primary particle diameter) of metal oxide microparticle (E) composition is preferably below 100nm, more preferably Below 30nm.When it is more than 100nm, there is the transparent tendency for the film that infringement is obtained.

Disperse product as commercially available silicon dioxide microparticle, as colloidal silica, methanol silica can be enumerated Colloidal sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, MIBK-ST, ST-UP, ST-OUP, ST-20, ST-40, ST- C, ST-N, ST-O, ST-50, ST-OL etc. (more than, Nissan Chemical Ind Ltd's system), OSCAL series, ELECOM series (more than, wave catalyst chemical conversion Co. Ltd. system day) etc..In addition, as powder silica, can enumerate：AEROSIL 130、 AEROSIL 300, AEROSIL 380, AEROSIL TT600, AEROSIL OX50 etc. (more than, Japanese AEROSIL Co., Ltd. System), Sill index H31, H32, H51, H52, H121, H122 etc. (more than, Asahi Glass Co., Ltd's system), E220A, E220 Deng (more than, Japanese silica industry Co. Ltd. system), SYLYSIA470 (Fuji's silicea Co. Ltd. systems), SG Flake (Nippon Sheet Glass Co Ltd's system) etc..

In addition, disperseing product as alumina particulate, NANOBYK-3601, NANOBYK-3602, NANOBYK- can be enumerated 3610 grades (more than, BYK-Chemie Amada Co., Ltd.s system), as the isopropanol of aluminum oxide disperse product, AS- can be enumerated 150I etc. (Sumitomo Osaka Cement Co., Ltd.'s system), disperses product, can enumerating AS-150T, (Sumitomo is big as the toluene of aluminum oxide Slope cement Co. Ltd. system)；Disperse product as the toluene of zirconium oxide, HXU-110JC (Sumitomo Osaka cement strain formula meetings can be enumerated Society's system)；Disperse product as the powder such as aluminum oxide, titanium dioxide, tin oxide, indium oxide, zinc oxide and solvent, commodity can be enumerated Name：Nanotec (Asahi Chemical Ind's system) etc..

Wherein, with regard to ELECOM V-8802 and ELECOM V-8804 (more than, wave day catalyst chemical conversion Co. Ltd. system) and The dispersiveness of particulate in speech, masking liquid is high, and the transparency or hardness, the marresistance of obtained film are further improved, therefore excellent Choosing.

The marresistance of film is further improved sometimes through cooperation (E) composition.For the usage amount of (E) composition, Relative to the parts by weight of (A) composition 100, more preferably preferably 0~100 parts by weight, 0~50 parts by weight.(E) use of composition When amount is more than 100 parts by weight, there is a situation where the situation for the transparency reduction that can not form film or film.

Cycloaliphatic epoxy (D) or metal oxide microparticle (E) do not give harmful effect to the hardness of film, because This, even if with condensation product (A) while in the presence of also having no problem.Condensation product (A), cycloaliphatic epoxy (D) and metal oxidation More than the 60 weight % of total solid component concentration preferred composition weight of thing particulate (E), more preferably more than 70 weight %, Even more preferably more than 80 weight %, most preferably particularly preferred more than 90 weight %, more than 95 weight %.But, with base Material it is closely sealed in, solvent be also it is important, therefore, consider adaptation viewpoint when, condensation product (A), alicyclic epoxy close Total solid component concentration of thing (D) and metal oxide microparticle (E) preferably below weight % of more than 30 weight % 80, it is more excellent Select more than 40 weight % below 80 weight %, even more preferably below the weight % of more than 50 weight % 80, particularly preferred 60 weight Measure below the weight % of more than % 80.When it is more than 80 weight %, the adaptation with base material is reduced sometimes.

＜ (F) photosensitizers ＞

, can be to improve (B) composition or (C) composition in addition, in the active energy ray-curable composition of the present invention Photosensitive purpose uses photosensitizer as needed.For photosensitizer, it can absorb in (B) composition or (C) used In composition the photosensitizer of the light of nonabsorbable wavelength domain be it is more effective, therefore, the absorption with (B) composition or (C) composition Overlapping few photosensitizer of wavelength domain is advisable.

As photosensitizer, it is not particularly limited, can enumerates for example：Anthracene derivant, benzophenone derivates, thioxanthones spread out Biology, anthraquinone derivative, benzoin derivatives etc..Wherein, oxidizing potential is low, participate in the singlet or triplet state of electronics movement The high photosensitizer of excitation energy be preferable, from the viewpoint of photo-induced electron donability, preferably anthracene derivant, thioxanthene Ketone derivatives and benzophenone derivates.More specifically, it can enumerate：9,10- dialkoxies anthracene, 2- alkyl thioxanthones, 2,4- Dialkyl group thioxanthones, 2- alkyl-anthraquinones, 2,4- dialkyl group anthraquinone, p, p '-aminobenzophenone, 2- hydroxyl -4- alkoxy hexichol Ketone, benzoin ether etc..More specifically, it can enumerate：It is anthrone, anthracene, 9,10- diphenylanthrancenes, 9- ethyoxyls anthracene, Bi, perylenes, dizzy Benzene, phenanthrene, benzophenone, benzil, benzoin, 2- methyl benzoylbenzoates, 2- benzoylbenzoic acids butyl ester, benzoin ethyl Ether, benzoin-isobutyl ether, 9-Fluorenone, acetophenone, p, p '-tetramethyl-diaminobenzophenone, p, p '-tetraethyl aminodiphenyl Ketone, CTX, ITX, 2,4- diethyl thioxanthones, phenthazine, acridine orange, benzoflavine, hair are yellow Element-T, 2- nitrofluorenes, 5- nitros acenaphthene, benzoquinones, the chloro- 4- nitroanilines of 2-, N- acetyl group-paranitroanilinum, paranitroanilinum, N- Acetyl group -4- nitros-naphthalidine, picramide, anthraquinone, 2- EAQs, 2- tert-butyl groups anthraquinone, 1,2 benzae thracene quinone, 3- methyl - (5,7- benzhydryloxycarbonyls are fragrant for 1,3- diaza -1,9- benzanthrones, dibenzalacetone, 1,2- naphthoquinones, 3,3 '-carbonyl-bis- Legumin), 9,10- dibutoxies anthracene, 9,10- dipropoxy anthracenes etc..Photosensitizer can be used alone, can also and with 2 kinds with On.

Suitably adjusted according to the curing rate of target using addition during photosensitizer, relative to photoacid generator (B) more than 100 parts by weight, preferably 0.1 parts by weight, more than more preferably 0.5 parts by weight.Additionally, it is preferred that below 10 parts by weight, it is more excellent Select below 5 parts by weight.When the addition of photosensitizer is less than 0.1 parts by weight, it is difficult to the effect of target photosensitizer is obtained, when it During more than 10 parts by weight, there is film coloring or cause the elevated tendency of cost.

＜ active energy ray-curable compositions ＞

The present invention active energy ray-curable composition contain above-mentioned (A), (B) composition, as needed containing (C), (D), (E), (F) composition, but in order to adjust physical property, further can suitably coordinate various additives.For example, can add inorganic Pigment or organic pigment, plasticizer, dispersant, wetting agent, tackifier, defoamer etc. are generally used for the additive of coating.

In addition, bonding solvent can be matched somebody with somebody in the active energy ray-curable composition of the present invention.As solvent, without special Limitation, the base material used be plastics in the case of, the solvent resistance of most base material is low, it is therefore preferable that methyl iso-butyl ketone (MIBK) or The esters such as the alcohols such as the ketones such as DIBK, butanol or isopropyl alcohol, butyl acetate or isopropyl acetate, diethylene glycol methyl The ethers such as ether or methyl proxitol.Particularly in terms of base material is not damaged, more than the 30 weight % of total solvent are preferably used Ether series solvent.It is total relative to (A) composition, (B) composition, (C) composition, (D) composition and (E) composition as the use level of solvent Measure 100 parts by weight, more preferably preferably 0~300 parts by weight, 0~150 parts by weight.When the use level of solvent is more than 300 parts by weight, There is a possibility that to damage base material as described above, thus it is not preferred.

As the present invention active energy ray-curable composition preparation side, be not particularly limited, can enumerate for example with The composition stated is closed, shading is carried out if necessary, is mixed with hand power stirring device or static mixer, or using planetary Agitator or dissolving rod, roller, kneader etc. are kneaded under normal temperature or heating, or make composition molten using solvent suitable on a small quantity Solve and carry out the usual way such as mixing.

＜ solidfied materials ＞

The present invention solidfied material be make the present invention active energy ray-curable composition solidification obtained from.As entering The active energy ray irradiated during row solidification, can enumerate visible ray, ultraviolet, infrared ray, X-ray, alpha ray, β rays, delta ray Deng, but from reaction speed is fast, active-energy beam generating apparatus it is comparatively cheap from the aspect of, most preferably ultraviolet.It is used as activity The exposure of energy line, preferably 50mJ~10,000mJ/cm²Accumulated light, more preferably 100mJ~2,000mJ/cm²Accumulation Light quantity.The exposure of active energy ray is less than 50mJ/cm²When, light quantity is few, therefore, and the time is spent in solidification sometimes, productivity ratio It is deteriorated.On the other hand, the exposure of active energy ray is more than 10,000mJ/cm²When, it can not solidify well-balancedly sometimes, or damage Base material.

Solidification temperature is not particularly limited, it is usually preferred to less than 100 DEG C, more preferably less than 80 DEG C, even more preferably Less than 50 DEG C.When being solidified at a temperature of higher than 100 DEG C, due to the line differential expansion between solidfied material and base material, therefore have can Can deformation increase.Particularly preferably solidified at room temperature.

＜ layered products ＞

The active energy ray-curable composition manufacture layered product of the present invention can be used.The layered product of the present invention passes through bag Make active-energy containing the process and irradiation active energy ray that the active energy ray-curable composition of the present invention is coated on to base material Line solidification compound is solidified to form the manufacture method of the process of curing overlay film to obtain.

As base material, it is not particularly limited, various base materials described later can be used.

The layered product of the present invention can be preferred for glass pane of the front panels such as notebook computer, automobile etc..

The present invention active energy ray-curable composition can be preferred for by such as metal, ceramics, glass, cement, Building, electrical home appliances, the industrial equipments of composition such as ceramic industry system base material, plastics, film, sheet material, timber, paper, fiber etc. are applied Dress.Particularly from the aspect of the irradiation easy degree of active energy ray, acrylic resin or makrolon can be preferred for The base materials such as the plastics such as resin, PET resin, film, sheet material.

As (A) composition of active energy ray-curable composition, silane compound (I), silane compound are being used (II-1) obtained from, being also hydrolyzed, be condensed with above-mentioned mol ratio using silane compound (II-2), use as needed In the case of condensation product, as base material, single layer of substrate material is preferably used., can be with as long as base material individual layer shape, is just not particularly limited For the base material being made up of multiple compounds.From it is effective using as active energy ray irradiate solidification it is advantage, when solidifying not Need from the viewpoint of hyperpyrexia, preferred resin base material can enumerate such as acrylic resin or polycarbonate resin, PET resin Deng base materials such as plastics, film, sheet materials.

As acrylic resin base material, it can enumerate：SUMIPEX, Technolloy (more than, firmly change acryl and sell strain formula meeting Society's system), ACRYPLEN, acrylite (more than, Mitsubishi's rayon Co. Ltd. systems), paragraph, comoglas (more than, strain Formula commercial firm Kuraray system), DELAGLAS, DELAPRISM (more than, Asahi Chemical Industry's techno-plas Co. Ltd. systems), KanaseLite (kanase Industrial Co., Ltd system) etc..

As polycarbonate resin substrate, it can enumerate：CARBOGLASS (Asahi Glass Co., Ltd's system), IRIS makrolon (Supreme Being people is melted into by sheet material (IRISshinyo Co. Ltd. systems), Iupilon (Mitsubishi Gas Chemical Co. Ltd. system), PAN RIGHT Co. Ltd. system), polycarbonate plate (Takiron Co. Ltd. systems), policaace (Sumitomo Bakelite Co., Ltd. System), polycarbonate plate (Ricoh KK's system), PC Miller (Co., Ltd. water chestnut shake system) etc..

As PET resin base material, it can enumerate：Petace (Sumitomo Bakelite systems), ESTELLA, ESTELLA SUPER (Ricoh KK's system), PETERS (Mitsubishi Plastics Inc's system), Petech (Takiron plants of formula meetings Society's system), minellon (minellon chemical conversion industries Co. Ltd. system), PolytecA-PET sheet materials (Polytec Co., Ltd. System), A-PET resin sheets (Teijin Chemicals, Ltd.'s system), Lumirror (Dongli Ltd.'s system), Cosmo Shine (east Paj Co. Ltd. system) etc..

Even if it should be noted that being multi-layer substrate, respective linear expansion coefficient or hygroscopicity are also almost identical, as long as The base material of warpage is also nearly free from after environmental test is carried out, it is possible to similarly preferably use.

Thickness preferred below the 5mm, more preferably below 4mm, further preferred below 3mm of single layer of substrate material.Single layer of substrate material When thickness is more than 5mm, the rigid influence of base material itself is big, is difficult to be influenceed by convergent-divergent caused by film.

It is used as coating thickness, preferably 1~100 μm.When coating thickness is less than 1 μm, exist easily by plastics, film, piece The influence of the base materials such as the material hardness of itself, the tendency of sufficient hardness can not be obtained, when coating thickness is more than 100 μm, there is work Property energy line, which can not be arrived, to be reached deep and solidifies slack-off tendency.Coating thickness is being set in the case of more than 100 μm, preferably It is divided into and repeats application and the irradiation of active energy ray for several times.

Embodiment

Hereinafter, based on embodiment, the present invention will be described, but the present invention is not limited by embodiment.

Raw material used in embodiment, comparative example are as described below.

A-186：Step the Japanese contract commercial firm system of figure new high-tech material, β-(3,4- epoxycyclohexyls) ethyl trimethoxy silane

A-187：Step the Japanese contract commercial firm system of figure new high-tech material, 3- glycidoxypropyltrime,hoxysilanes

CELLOXIDE2021P：Co., Ltd.'s Daicel system, 3,4- epoxycyclohexyl-methyls -3 ', 4 ' -7-oxa-bicyclo[4.1.0 carboxylic Acid esters

ELECOM V-8804：Wave day catalyst chemical conversion Co. Ltd. system, Organic silica sols (silica it is flat Equal particle diameter：About 10nm) propylene glycol monomethyl ether solution

CPI-101A：San-apro Co. Ltd. systems, triaryl matte SbF₆The polypropylene carbonate ester solution of salt

A-174：Step the Japanese contract commercial firm system of figure new high-tech material, γ-methacryloxypropyl trimethoxy silane

A-171：Step the Japanese contract commercial firm system of figure new high-tech material, vinyltrimethoxy silane

KBM-5103：Shin-Etsu Chemial Co., Ltd's system, 3- acryloxypropyl trimethoxy silanes

Magnesium chloride：Wako Pure Chemical Industries, Ltd.'s system, superfine

1- methoxy-2-propanols：Co., Ltd.'s Daicel system

Methanol：Mitsubishi Gas Chemical Co. Ltd. system

Base material A：PET film (Co. Ltd. system, Cosmo ShineA4300,250 μm of thickness spin in Japan)

Base material B：Acrylic acid sheet material (firmly changes acryl and sells Co. Ltd. system, TechnolloyS001, thickness 0.5mm)

Base material C：Teijin Chemicals, Ltd.'s system, PAN RIGHTAD-5503 (are configured to 1.0mm thick by polycarbonate sheet Sheet material)

(synthesis example 1-10)

(unit of use level is the composition of addition table 1 in the reactor for having mixer, thermometer, reflux cooler Parts by weight), 60 DEG C are warming up to, after stirring 5 hours, decompression devolatilization is carried out at 60 DEG C, condensation product is obtained.

Acetone-d6 is used for solvent, obtained condensation product is determined with NMR, the OR with silicon atom Direct Bonding is calculated³Base Molal quantity Y and the silicon atom Direct Bonding having with the silane compound of raw material OR³The ratio between the molal quantity X of base Y/X.In addition, with¹HNMR determines obtained condensation product, calculates the survival rate of 3,4- epoxycyclohexyls.Weight average molecular weight is measured (table 1) with GPC.

[table 1]

(embodiment 1-8, comparative example 1-8)

Coordinate (unit of use level is parts by weight) as Table 2,3, prepare coating liquid.It should be noted that closing The condensation product and A-186 obtained into example 1-10 is used uses propylene glycol monomethyl ether in the way of non-volatile content turns into 50 weight % The material diluted.Turn into about 20 using bar coater No.40, with dry film thickness on PET film (150mm × 100mm × 250 μm) μm mode be coated with the coating liquid, in order at 80 DEG C remove solvent 2 minutes and be dried.Then, in atmosphere using height Medium pressure mercury lamp, with 240mW, 310~390nm of wavelength accumulated light turn into 1000mJ/cm²Mode irradiate active energy ray, Thus solidified, test film is made.

Each physical property (table 2,3) of evaluation test piece.

[table 2]

[table 3]

(evaluation of physical property)

Thickness

After irradiation active energy ray 7 days, it is measured using film thickness gauge, subtracts the thickness of base material and calculate.

Hardness

After irradiation 7 days, pencil hardness is evaluated according to JIS K5600.

Marresistance

After irradiation 7 days, using erasing rubber abrasiometer (Co., Ltd.'s trimmed book makes made), apply 500g/cm²'s Load, makes steel wool #0000 come and go 1000 times, and observation residues in the bar number of the wound of film.

○：Completely without or the wound of less than 3

△：The shallow wound of 4 to 10

×：Hinder wound more than 10 or deep

Impact resistance

After irradiation 7 days, measure makes 22g steel ball land in 10cm²Test film center, when being cracked on film Height.

Warpage

After irradiation active energy ray 7 days, layered product is taken care of 72 hours in 85 DEG C of 85% hot and humid machine, 4 are taken out After hour, it is arranged at film as mode above on horizontal platform.Respectively to above layered product 4 summits determine from To the distance of vertical direction above platform, its average value is calculated.The surface side warpage of layered product is being coated with (below layered product Face emersion of the angle from platform) in the case of, positive value is set to, in the case where its is opposite, negative value is set to.

It should be noted that PET film base material is individually 0mm in the result evaluated with the conditions of.

In embodiment 1-8, confirm：When making the solidification compound solidification containing condensation product (A), even if dry film thickness is More than 10 μm, crack is not also produced, shows excellent performance in hardness, marresistance, any one of impact resistance.With this Relatively, in comparative example 1,6-8, when making β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane solidification, with alkoxyl silicone The reaction of alkane and produce cure shrinkage, crack is produced on film, it is thus impossible to determine thickness and various physical property.In addition, than Compared with example 2, hardness, marresistance are insufficient.In comparative example 3, the glycidoxy that condensation product has and epoxy hexamethylene Base is compared, and cationically polymerizable is low, therefore, and hardness, marresistance turn into the result being deteriorated significantly compared with embodiment.Than Compared with example 4, the use level of the silane compound of the epoxycyclohexyl with the raw material as condensation product is few, it is impossible to obtain sufficiently Crosslink density, therefore, hardness, marresistance turn into the result being deteriorated compared with embodiment.In comparative example 5, using light certainly Solidify polyfunctional acrylic ester by base producing agent, but compared with embodiment, can obtain cure shrinkage significantly and impact resistance The result of variation.

Learn in addition：In embodiment 1~8, compared with comparative example 5, warpage can be suppressed.

(synthesis example 11-23)

The composition of addition table 4 in the reactor for having mixer, thermometer, reflux cooler, is warming up to 130 DEG C, stirs Mix after 5 hours, decompression devolatilization is carried out at 70 DEG C, condensation product is obtained.

On obtained condensation product, mol ratio Y/X, the survival rate of 3,4- epoxycyclohexyls and weight average molecular weight are determined.

[table 4]

(embodiment 9-20, comparative example 9-14)

Coordinate (unit of use level is parts by weight) as shown in Table 5,6, prepare coating liquid.It should be noted that closing The condensation product obtained into example 11~23 uses what is diluted in the way of non-volatile content turns into 50% with propylene glycol monomethyl ether Material.210mm × 297mm various base materials (embodiment 20 be acrylic acid sheet material, embodiment 21 be polycarbonate sheet, its In addition be PET film) on using bar coater No.30, by dry film thickness turn into about 20 μm in the way of be coated with the coating liquid, in order to 80 Solvent 2 minutes is removed at DEG C and is dried.Then, in atmosphere using high-pressure mercury-vapor lamp, with 240mW, wavelength 310~ 390nm accumulated light turns into 1000mJ/cm²Mode irradiate active energy ray, thus solidified, test film be made.

Each physical property (table 5,6) of evaluation test piece.On warpage, the value after maintenance in 7 days is also evaluated.

[table 5]

[table 6]

In embodiment 9-20, confirm：When making the solidification compound solidification containing condensation product (A), in hardness, scratch resistance Show excellent performance in property, any one of warpage.

On the other hand, in comparative example 9,10, when being solidified, produce and received with the solidification of acrylate-based polymerization Contracting, produces very big warpage.

In addition, in comparative example 11, the alkoxy that remaining 50% is not hydrolyzed in condensation product (A) is making layer Reacted during stack, therefore, compared with Example 9, greatly produce cure shrinkage and warpage.

In comparative example 12 and 13, the quantity of the methylacryloyl in condensation product (A) is excessive, therefore, produces with first The cure shrinkage of the acrylate-based polymerization of base, produces very big warpage.

It is therefore, same with comparative example 11 due to remaining 40% alkoxy in condensation product (A) in comparative example 14, significantly Ground produces cure shrinkage and warpage, in addition, when preparing condensation product, using acid catalyst, epoxycyclohexyl thus is entered into water-filling Solution, so, compared with Example 9, hardness, marresistance are also reduced.

Claims (17)

1. a kind of active energy ray-curable composition, it contains：Weight average molecular weight is less than 20,000 condensation product (A) and light Acid agent (B),

Wherein, the condensation product (A) obtains as follows：The silicon with hydrolyzable silyl group for representing following logical formula (I)s Hydride compounds (I) are hydrolyzed, are condensed in the basic conditions,

R¹-(SiR² _a(OR³)_3-a) (I)

In formula, R¹The alkyl for the carbon number 1~10 that be instead of for end by 3,4- epoxycyclohexyls, R²It is separately hydrogen In the aralkyl of atom or alkyl selected from carbon number 1~10, the aryl of carbon number 6~25 and carbon number 7~12 1 valency alkyl, R³It is separately hydrogen atom or the alkyl of carbon number 1~10；A is 0~2 integer,

The OR with silicon atom Direct Bonding that condensation product (A) has³The molal quantity Y of base is relative to the raw material as condensation product (A) The OR with silicon atom Direct Bonding that silane compound (I) has³The ratio between the molal quantity X of base Y/X is less than 0.2.

2. active energy ray-curable composition as claimed in claim 1, wherein, condensation product (A) is obtained as follows：Make silicon The silane compound (II) with hydrolyzable silyl group that hydride compounds (I) are represented with following logical formula (II)s is with silane compound (II) mode that the mol ratio relative to silane compound (I) is less than 2.0 is hydrolyzed, is condensed in the basic conditions,

R⁴-Si(OR³)₃ (II)

In formula, R⁴Substituted or unsubstituted alkyl, alkenyl and substituted aryl selected from carbon number 1~10, and R⁴For not Group with 3,4- epoxycyclohexyls, R³It is separately hydrogen atom or the alkyl of carbon number 1~10,

The OR with silicon atom Direct Bonding that condensation product (A) has³The molal quantity Y of base is relative to the raw material as condensation product (A) The OR with silicon atom Direct Bonding that silane compound (I) and silane compound (II) have³The ratio between the molal quantity X of base Y/X For less than 0.2.

3. active energy ray-curable composition as claimed in claim 1, wherein, R¹For β-(3,4- epoxycyclohexyls) ethyl.

4. active energy ray-curable composition as claimed in claim 2 or claim 3, wherein, condensation product (A) is obtained as follows：

As silane compound (II), the silane compound with hydrolyzable silyl group represented using following formulas (II-1) (II-1) and following formulas (II-2) represent the silane compound (II-2) with hydrolyzable silyl group, with silane chemical combination Thing (II-1) is 0.03~1.0 relative to the mol ratio of silane compound (I), silane compound (II-2) is relative to silane chemical combination The mol ratio of thing (I) is hydrolyzed, is condensed for 0~1.0,

R⁵-Si(OR³)₃ (II-1)

In formula, R⁵The alkane for the carbon number 1~10 that instead of selected from (methyl) acryloyl group, glycidyl or by mercapto The alkenyl and substituted aryl of base, carbon number 2~10, and R⁵For the group without 3,4- epoxycyclohexyls, R³Respectively The alkyl of hydrogen atom or carbon number 1~10 independently is,

R⁶-Si(OR³)₃ (II-2)

In formula, R⁶Alkyl and carbon number 1 selected from amino, phenyl, cyclohexyl or the carbon number 1~10 replaced by chlorine ~10 unsubstituted alkyl, and R⁶For the group without 3,4- epoxycyclohexyls, R³It is separately hydrogen atom or carbon atom The alkyl of number 1~10.

5. such as active energy ray-curable composition according to any one of claims 1 to 3, it also contains alicyclic epoxy Compound (D).

6. active energy ray-curable composition as claimed in claim 5, wherein, cycloaliphatic epoxy (D) is 3,4- Epoxycyclohexyl-methyl -3 ', 4 '-epoxycyclohexane carboxylate.

7. such as active energy ray-curable composition according to any one of claims 1 to 3, it is also containing average grain diameter Below 100nm metal oxide microparticle (E).

8. active energy ray-curable composition as claimed in claim 7, wherein, metal oxide microparticle (E) is titanium dioxide Silicon particle.

9. such as active energy ray-curable composition according to any one of claims 1 to 3, wherein, relative to condensation product (A) 100 parts by weight, contain the parts by weight of photoacid generator (B) 0.05~30, the parts by weight of cycloaliphatic epoxy (D) 0~100 and metal The parts by weight of oxide fine particle (E) 0~100.

10. such as active energy ray-curable composition according to any one of claims 1 to 3, wherein, photoacid generator (B) is Aromatic series sulfonium salt or aromatic series iodineSalt.

11. active energy ray-curable composition as claimed in claim 10, wherein, the counter anion of photoacid generator (B) For fluorophosphoric acid ester series anion or fluorine metaantimmonic acid ester series anion.

12. such as active energy ray-curable composition according to any one of claims 1 to 3, it also contains photosensitizer (F)。

13. active energy ray-curable composition as claimed in claim 12, wherein, photosensitizer (F) is anthracene derivant, thiophene Ton ketone derivatives or benzophenone derivates.

14. a kind of solidfied material, its make the active energy ray-curable composition any one of claim 1~13 solidify and Obtain.

15. a kind of manufacture method of layered product, this method includes：

By the active energy ray-curable composition any one of claim 1~13 be coated on base material process and

Irradiation active energy ray makes the process that active energy ray-curable composition is solidified to form curing overlay film.

16. a kind of layered product, it is obtained by the manufacture method described in claim 15.

17. layered product as claimed in claim 16, active energy ray-curable composition described in its usage right requirement 4 and Single layer of substrate material.